JP2008509876A - Method for producing monolithic porous carbon disks from aromatic organic precursors - Google Patents

Abstract

【Task】
[Solution]
Disclosed is a method for producing monolithic and metal-doped monolithic porous carbon disks derived from powdered prepolymer organic precursors comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole. The powder is compacted (compressed) into a disk and pyrolyzed to form the desired carbon disk. Carbon is also added to the prepolymer organic precursor to prepare a porous carbon-carbon composite disc.
[Selection figure] None

Description

Description This application is a continuation-in-part of US application Ser. No. 10 / 919,450, filed Aug. 16, 2004.

TECHNICAL FIELD The present invention relates to polyimide, polybenzimidazole, or both as organic precursors for producing monolithic porous carbon having a density below 1.0 g / cc or equal to 1.0 g / cc. And a process for producing monolithic porous carbon from either powdered polyimide or polyimidazole, or both polyimide and polybenzimidazole. The present invention further provides a process for producing monolithic porous carbon derived from either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole precursors, with one or more metals dispersed in the precursor. About. The present invention further provides a carbon-carbon synthesis prepared from a precursor comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole, and powdered and / or fibrous activated carbon. It relates to the manufacturing process of goods.

BACKGROUND ART Monolithic porous carbon with interpenetrating pore structure, high density, high surface area, suitable pore size, and well-defined pore size distribution is used in lithium batteries, electrochemical capacitors, fuel cells, and other electrical devices. It is highly desirable as an electrode material for chemical devices. While it will be appreciated that other such products can be made from porous carbon, the following description is targeted at disk products.

  One method for producing monolithic porous carbon disks is by sol-gel technology. Sol-gel technology generally consists of producing a gel from a solution and drying the gel with minimal shrinkage of the gel. By pyrolyzing this thin gel film, a porous monolithic carbon disk is produced. As an electrode material for supercapacitors, RF carbon aerogels currently on the market are derived from organic precursors of resorcinol and formaldehyde. RF carbon airgel provides high surface area and narrow pore size distribution. However, the potential market for RF carbon aerogels as electrodes and materials for ultracapacitors and supercapacitors is severely limited by the low operating voltage of this capacitor (<= 5V) and the high manufacturing cost of monolithic RF carbon aerosol materials Has been.

  Another method for producing a monolithic porous carbon disk is from a porous polymer precursor powder by compressing the porous polymer precursor into a monolith disk and then pyrolyzing. There are two obstacles to this method. One is the compressibility of the polymer precursor, and the other is the difficulty of maintaining an interpenetrating network of pores during the compression process. US Pat. No. 6,544,648 discloses a monolithic carbon disk by compressing a carbon black powder having a high surface area under vacuum at a temperature of 800 ° C. or above 800 ° C. and a pressure of 3000 psi or 3000 psi. A process for manufacturing is disclosed. This method produces a carbon disk with more undesirable micropores with a pore size 2 nm smaller than the carbon disk by the sol-gel method. Compression of carbon powder under vacuum at 800 ° C. has severe technical challenges and high production costs.

  However, another method for producing monolithic porous carbon is from carbon black powder solidified in a matrix-like carbonized synthetic resin. US Pat. Nos. 5,776,633; 5,172,307; and 5,973,912 describe processes for producing such porous carbon-carbon composites. In these patents, the synthetic resin is a phenolic resin. This method has an advantage of low cost by using an inexpensive carbon black powder, but it is difficult to keep the pores of the synthetic resin, and therefore the pore surface area ratio is low.

  With the problems and deficiencies of the prior art in mind, the object of the present invention is to provide a monolithic porous carbon with high surface area, high pore volume, high surface activity, well-defined pore structure and morphology, and good mechanical properties Is to provide a disc. It would also be desirable to provide a manufacturing process for such monolithic porous carbon disks that is significantly less costly than those currently on the market.

  In addition, other objects and advantages of the present invention will be in part apparent from the specification and in part will be apparent visually.

DISCLOSURE OF THE INVENTION The present invention provides a process for the production of monolithic porous carbon, such as a disc, derived from an aromatic organic precursor group comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole. To do. The process includes: (1) preparing a powdery organic precursor; (2) compacting the powder into a monolith; (3) producing a monolithic porous carbon product such as a disk by pyrolysis. And a step of.

  The present invention describes a process for producing a monolithic porous carbon disk doped with a transition metal from a group of aromatic organic precursors comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole, and a metal compound. Further provide. The process includes: (1) preparing a powdery precursor doped with a metal compound in situ; (2) compacting the powder into a monolith; (3) monolithic like a disk; And pyrolytically producing a porous carbon product.

  The present invention includes the precursor of the present invention, and powder, fiber, nanotube, giant ball (C60, C70, or other), fullerene-like carbon, or a mixture thereof. A process for producing a porous carbon-carbon composite is further provided. Preferably, the carbon used in the process is activated carbon powder and activated carbon fibers. The process includes: (1) preparing a powdered or viscose-like precursor; (2) mixing with carbon and precursor, removing the solvent frame after mixing; 3) compacting the mixture into a monolith; and (4) producing a porous carbon-carbon composite by pyrolysis.

  The organic precursor of the present invention has a nitrogen-containing heterocyclic structure that connects monomer units using a few flexible links or hinges into a rod-like molecular chain structure. The chain structure of the precursor is made of either a straight chain, a three-dimensional network, or a hiber branch chain structure. One group of precursors comprises a polyimide having an imide group in the molecular structure. Another group of precursors comprises polybenzimidazoles having benzimidazole groups in the molecular structure. Yet another group of precursors comprises both polyimides and polybenzimidazoles that have both imide and benzimidazole groups in the molecular structure.

  The monolithic porous carbon disk produced from the present invention is a fiber or fiber pad or other additive by incorporating fibers, inorganic or organic particles, fiber pads or other additives during the compression molding process. It can be further reinforced with objects.

  The precursor powder may be further combined with other additives in addition to carbon before being consolidated into a monolith. Such additives include oxidative transition metal powders, organic particles, inorganic particles, graphite fibers or flakes, metal fibers, porous substrates including membranes, metal mesh, carbon cloth, carbon felt, foams, and phenolic resins. And polymer resins such as commercially available polyimide resins.

  The precursor prepared from the aromatic organic monomer of the present invention may comprise other components of molecular chain structure such as polybenzimidazole, polyamide, polyetherimide, siloxane, or silica, but preferably 50 weights Having a polyimide and aromatic organic composition greater than or equal to%.

によって、表すことができる。 Polyimide and polybenzimidazole have the formula:

Can be represented by

Here, A1 and A4 are
Bifunctional phenyl, bifunctional biphenyl, optionally substituted difunctional aryl, selectively substituted difunctional alkylene, selectively substituted difunctional heteroaryl, or combinations thereof;
Represents
A2 and A5 are
Trifunctional phenyl, biphenyl, an optionally substituted trifunctional aryl group, or an optionally substituted heteroaryl group;
Represents
A3 is
Multifunctional phenyl having a number of functional groups greater than or equal to 2 Multifunctional biphenyl having a number of functional groups greater than or equal to 2, Number of functional groups greater than or equal to 2 Selectively substituted polyfunctional aryl having a number of functional groups selectively substituted polyfunctional alkylene having a number greater than 2, or equal to 2 A selectively substituted polyfunctional heteroaryl having, or a combination thereof;
Represents
n1, n2 and n3 are greater than 1 or equal to 1; (y + 2) is greater than 2 or equal to 2.

  One application of the present invention is to provide novel carbon electrodes for electrochemical capacitors, batteries, and fuel cells.

  Another application of the present invention is to provide novel composites of carbon and transition metal oxides such as MnO2 as electrodes for lithium batteries or hybrid-battery / electrochemical capacitor systems.

  Another application of the present invention is to provide catalytic carbon supports for fuel cells and electrochemical water purification systems.

  Although the present invention has been particularly described with certain preferred embodiments, it is clear that many variations, modifications, and variations will be apparent to those skilled in the art from the foregoing description. Accordingly, the claims are intended to cover all alternatives, modifications, and variations that fall within the precise scope and spirit of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The features of the invention believed to be novel and the characteristic elements of the invention are set forth with particularity in the appended claims. The drawings are for illustrative purposes only and are not to be reduced.

  However, the invention itself, both in terms of construction and method of operation, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.

DETAILED DESCRIPTION OF THE INVENTION In describing the preferred embodiment of the present invention, reference is made to FIGS. Here, the same reference numerals are assigned to the same features of the present invention.

4). DETAILED DESCRIPTION OF THE INVENTION In a first aspect, the present invention provides an organic precursor for producing monolithic porous carbon having a surface area greater than 500 m ² / gram, or greater than 500 m ² / gram, and sufficiently high mechanical strength. As a body, a manufacturing process for a monolithic disk comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole is provided.

  The aromatic monomers for preparing the polyimide precursors of the present invention are preferably in the following groups: aromatic dianhydrides, aromatic diamines, and optionally aromatic polyamine compounds having more than two amine functional groups; or Aromatic tetracarboxylic acids, aromatic diamines, and optionally aromatic polyamine compounds having more than two amine functional groups; or aromatic tetracarboxylic acids, aromatic diamines, and optionally more than two An aromatic polyamine compound having an amine functional group; or an aromatic dianhydride, a diisocyanate having more than two amine functional groups, and an aromatic isocyanate comprising a polyisocyanate. The

  The aromatic monomers for the preparation of the polybenzimidazole precursor are preferably the following monomer groups: aromatic dialdehydes and aromatic tetraamines; or diesters of aromatic dicarboxylic acids and aromatic tetraamines; or aromatic dicarboxylic acids and aromatic tetraamines. , Is selected from one of the following:

  Precursors comprising either polyimide or polybenzimidazole or both polyimide and polybenzimidazole can be synthesized from monomers either in the presence of a solvent or in a molten state, preferably by the following procedure.

・ Procedure 1
Mix all ingredients in the presence of solvent. This solvent is removed by distillation and a vacuum is applied if necessary to form a homogeneous mixture in powder form. Further chemical reactions to produce non-melt and non-melt high molecular weight polymer materials proceed after solvent removal or after compacting the powder such as a disk into a monolith.

・ Procedure 2
To produce the precursor as a precipitate in either a precipitate or gel form, a condensation reaction of aromatic monomers is performed in solution. The precipitate is a precipitated powder or a film that has been precipitated onto another solid phase substrate. The solvent in the precursor is removed by distillation and if necessary a vacuum is applied. The precursor is further pulverized into fine powders or porous particles, and if necessary, filtered through a sieve.

・ Procedure 3
In order to form a solid-form precursor, the aromatic organic precursor is heated to a molten state while stirring. Sometimes evaporation of by-products such as low molecular weight alcohol or water creates bubbles instead of dense solids. This precursor is further pulverized into fine powders or porous particles, and if necessary, filtered through a sieve.

  The polyimide precursor is preferably an aromatic diamine and an aromatic tetracarboxylic dianhydride, or an aromatic diamine and a tetracarboxylic acid, or an ester of an aromatic diamine and a tetracarboxylic acid, or an aromatic isocyanate and an aromatic tetra It is a condensation product of carboxylic dianhydride. Optionally, a small amount of a polyamine compound having more than two amine functional groups replaces some aromatic diamines, resulting in chemical cross-linking to the polyimide precursor. Therefore, the polyimide precursor may have a linear molecular structure, a hyperbranched molecular structure, or a three-dimensional network molecular structure. The synthesis of the polyimide precursor generally proceeds to the synthesis of poly (amic acid) and then imidized to form the polyimide.

  Polyimide precursors can be synthesized by any of Procedures 1 to 3 using diamine and polyamine compounds and aromatic amine monomers including esters of acids or tetracarboxylic acids. In Procedure 1, the monomer and other additives are dissolved in a solvent to form a clear solution. The precursor in fine powder form is either a homogeneous mixture of monomers or a mixture of low molecular weight oligomers of polyimide and poly (amic acid). In procedure 2, the monomer and other additives are dissolved in an organic solvent. The reaction is carried out with normal stirring at 100 ° C. or higher than 100 ° C., preferably at 150 ° C. or higher than 150 ° C. to produce a polyimide precipitate. The polyimide precursor is in the form of either a precipitated powder or a gel. If necessary, a vacuum is applied and the solvent is distilled off from the product. In Procedure 3, preferably an ester of a tetracarboxylic acid and an aromatic amine is the optimal monomer. The condensation reaction in the molten state of the monomer releases phenol or alcohol molecules in the gas phase to produce a rigid polyimide foam. The product is further crushed to produce a polyimide powder.

  Using an aromatic dianhydride and an aromatic amine monomer comprising a diamine and a polyamine, two steps are: synthesizing a poly (amic acid) and imidizing it to form a polyimide. Synthesis of the polyimide precursor is carried out by the procedure 2. The synthesis of poly (amic acid) is carried out by stirring normally for several hours to overnight and dissolving the monomer and other additives in an organic solvent at ambient temperature, either a precipitated powder or a viscose solution or gel To produce a product of any of the shapes. Polyimide (amidic acid) is imidized to form a polyimide by either chemical imidization at ambient temperature or thermal imidization at high temperature.

  Chemical imidization is performed by adding a dehydrating agent to the poly (amic acid). In the case of poly (amic acid) in the form of a precipitated powder, a dehydrating agent is preferably added before the reaction solvent is removed from the system. In the case of poly (amic acid) in the form of a viscose solution, the addition of the dehydrating agent to the poly (amic acid) solution is carried out in such a way as to produce a polyimide precipitate upon reaction at ambient temperature. The solvent is removed from the polyimide precipitate by distillation.

  The dehydrating agent consists of either an acid anhydride or a mixture of an acid anhydride and an organic base. Preferred acid anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. Preferred organic bases include selectively substituted mono-, di-, trialkylamines, and optionally substituted pyridines.

  Thermal imidization is carried out at an elevated temperature.

  In the case of poly (amic acid) in the form of a precipitated powder, the solvent is removed by distillation and then at a temperature in the range of 50 ° C. to 500 ° C., preferably in the range of 100 ° C. to 400 ° C., preferably nitrogen or argon, etc. The poly (amidic acid) powder is heat imidized under the protection of the inert gas. In the case of poly (amic acid) in the form of a viscose solution or gel, imidization is carried out at a high temperature in the range of 50 ° C. to 400 ° C., preferably in the range of 100 ° C. to 250 ° C. Of polyimide. If necessary, a vacuum is applied and the solvent is removed by distillation.

  The synthesis of the polyimide precursor is preferably carried out according to procedure 1, using aromatic dihydrate and aromatic isocyanate including diisocyanate and polyisocyanate as organic precursor. In this procedure, the monomer and additive are mixed at ambient temperature, preferably in the presence of a dipolar aprotic organic solvent. Removal of the solvent produces a homogeneous mixture in powder form.

  While not excluding other synthetic procedures, preferably, the polyimide precursor comprises a tetracarboxylic dianhydride, an aromatic diamine, and optionally a fragrance of the polyamine compound according to Procedure 2 using a thermal imidization method. Prepared from family monomers. In this procedure, the reaction of the monomer and other additives is carried out in an organic solvent such as dimethylacetamide (DMAc) at ambient temperature with stirring for some time. Next, the temperature of the reaction system is raised to a range of 130 ° C. to 200 ° C., preferably 150 ° C. to 180 ° C., to produce polyimide as a precipitate. The solvent is distilled off to produce a dry polyimide precursor powder.

  The polybenzimidazole precursor is preferably an aromatic tetraamine and an aromatic ester of a dicarboxylic acid, or a condensation product of an aromatic tetraamine and an aromatic dialdehyde. Synthesis proceeds either in the molten state of the monomer or in the presence of a solvent.

  Using aromatic tetraamine and aromatic dialedide as aromatic monomers, two steps: synthesizing poly (azomethine) as an intermediate product in the presence of organic solvent and synthesizing poly (benzimidazole) The synthesis of polybenzimidazole is carried out according to the procedure 2 of Step. In this procedure, the reaction of the monomer of the organic solvent is carried out at a temperature in the range of −30 ° C. and ambient temperature to produce poly (azomethine) in either precipitated powder or viscose-like solution form. Poly (azomethine) is converted to polybenzimidazole by further reaction at a high temperature in the range of 50 ° C. to 350 ° C., more preferably in the range of 100 ° C. to 250 ° C. The solvent is removed from the system when the product is precipitated from the solvent before or after the second stage reaction at elevated temperature.

  Although not limited to synthesis in the presence of a solvent, the synthesis of polybenzimidazole using an aromatic tetraamine and a monomer of an ester of a dicarboxylic acid preferably proceeds by Procedure 3 in the monomer melt state. Stir vigorously and react at or above the melting temperature of the monomer so that gaseous phase phenol or water or alcohol by-products are released from the system to form a foam-like product. carry out. This product is crushed and further crushed to produce a polybenzimidazole precursor in the form of a porous powder.

  Precursors comprising both polyimide and polybenzimidazole segments in the molecular structure can be prepared, preferably in the presence of an organic solvent. The synthesis can be carried out by synthesizing either a polyimide or polybenzimidazole precursor before adding other precursor monomers to the reaction system. Or, before combining the two reactions into one reaction system, the reaction of polyimide and polybenzimidazole is carried out separately. Otherwise, if the reaction conditions are compatible, the two monomer sets are mixed simultaneously in the same reaction solution. However, such mixing is usually prohibited if relatively large amounts of flexible amide bonds are introduced into the molecular chain structure in order to significantly lower the glass transition temperature of the material.

  An alternative method for preparing monolithic porous carbon disks from precursors comprising both polyimide and polybenzimidazole is to mix both polyimide and polybenzimidazole precursor powders during the process of compacting the powders into monolithic disks. It is to be.

  Optionally, a precursor powder comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole, is further broken up into smaller particle sizes by shear stress and, if necessary, filtered through a sieve. The preferred particle size of the precursor for compression molding is in the range of 1 μm to 300 μm, more preferably in the range of 5 μm to 75 μm, and even more preferably in the range of 10 μm to 50 μm.

  As another option, precursor powders comprising either powdered polyimide or polybenzimidazole, or both polyimide and polybenzimidazole, are further thermally annealed at elevated temperatures before being compacted into disks. This annealing is carried out in the temperature range of 50 ° C. to 600 ° C., more preferably in the range of 50 ° C. to 500 ° C., for 20 minutes to 2 hours under vacuum or under the protection of an argon or nitrogen atmosphere.

In a second aspect, the present invention provides catalytic activity where the surface area of 500 m ² / gram, or greater than 500 m ² / gram, sufficiently high mechanical strength, and transition metal atoms are caged or complexed. Transition metal doped precursors comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole as organic precursors for producing transition metal doped monolithic porous carbon disks having a macrocyclic pyridine structure A monolithic porous carbon disk manufacturing process is provided.

  In a typical procedure, the transition metal compound in solution is added to the reaction system, to the dry precursor powder, or to the dry disk precursor. The solvent used for dissolving the transition metal is preferably the same solvent as the solvent for preparing the precursor. While not limited to the addition of the metal compound at any stage or at any stage during the preparation of the monolith disk including the synthesis steps of the condensation reaction and consolidation process, preferably the transition metal compound is added at an early stage of the procedure. Add. More preferably, the transition metal compound is mixed with the organic precursor in the presence of an organic solvent before proceeding with the synthesis of the precursor.

  Solvent removal in the precursor synthesis comprising either polyimide or polybenzimidazole or both polyimide and polybenzimidazole is carried out by distillation, preferably distillation under vacuum.

Suitable metals used in preparing the metal doped monolithic porous carbon of the present invention include, but are not limited to, elemental metals, organometallic compounds, coordinated inorganic compounds, metal salts, or any combination thereof. . Preferred metals are Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P, As, Li and combinations thereof are included. Exemplary transition metal compounds include cobalt chloride (CoCl ₂ ), iron chloride (FeCl ₃ ), nickel chloride (NiCl ₂ ), molybdenum chloride (MoCl ₅ ), hexachloroplatinic acid hydrate (H ₂ PtCl ₆ * xH ₂ O), copper chloride (CuCl ₂ ), tungsten chloride (WCl ₆ ), zirconia chloride (ZrCl ₄ ), cerium nitrate (Ce (NO ₃ ) ₃ ), ruthenium chloride (RuCl ₃ ), and hafnium chloride (HfCl ₄ ). included.

  Typically, the transition metal compound is present in the precursor in an amount of 0.01 wt% to 20 wt%, or more.

  In a third aspect, the present invention comprises: producing a powdered organic precursor comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole; under a pressure in the range of 3000 psi to 13000 psi; Consolidating the powder into a monolith; and pyrolyzing under the protection of an inert atmosphere; having a rod density less than or equal to 1.0 gram / cc A method for producing a monolithic porous carbon disk is provided.

  In a fourth aspect, the present invention provides: a powder of a transition metal dope precursor comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole; under a pressure in the range of 3000 psi to 13000 psi, A monolithic porous carbon having a rod density of less than or equal to 1.0 gram / cc comprising: a monolith compacted with porous precursor powder at ambient temperature; and pyrolysis under the protection of an inert atmosphere. A method for producing a monolithic porous carbon disk having one or more metals dispersed within the disk is provided.

  In a typical consolidation procedure, a rod density in the range of 0.4 g / c to 1.0 g / c, preferably 0.6 g / cc to 0.95 g / cc, with sufficiently high compression pressure and sufficient holding time. Before producing a monolithic disk having, a precursor powder is uniformly disposed on a support substrate such as a mold or a fiber pad.

  The thermal decomposition of the compression disk is carried out at a temperature in the range of 600 ° C. to 3000 ° C., more preferably 750 ° C. to 1500 ° C., under the protection of an inert gas atmosphere such as argon, nitrogen or carbon dioxide. Optionally, during pyrolysis, preferably at a stage after pyrolysis, the inert gas atmosphere may be changed to carbon dioxide to further activate the pore surface of the monolithic carbon disk. The heating rate should be slow enough to optimize the properties of the monolithic carbon.

  In a fifth aspect, the present invention comprises: thoroughly mixing the precursor, carbon, and other additives; removing the solvent in the mixture if a solvent is included in the mixture; Condensing the mixture into a monolith under pressure conditions to produce a homogeneous composition having a rod density of; and pyrolyzing under an inert atmosphere to produce a monolithic porous carbon disk. Including either polyimide or polybenzimidazole powder, or both polyimide or polybenzimidazole and activated carbon in fiber form, less than 1.0 gram / cc from the precursor, or 1.0 A process for producing a porous carbon-carbon composite having a rod density equal to grams / cc is provided.

  In a sixth aspect, the present invention relates to: the step of thoroughly mixing the organic precursor of the present invention, carbon, and other additives; and in the mixture if a solvent is included during mixing. Removing the solvent of; condensing the mixture into a monolith under pressure conditions to produce a homogeneous composition having a desired rod density; and producing a monolithic porous carbon by pyrolysis under an inert atmosphere A process for producing a porous carbon composite that incorporates other additives in addition to the carbon.

  Other additives include metal compounds, silica, powder, fibers, nanotubes, giant balls or fullerenes, graphitic carbon, metal oxides and metal carbides, commercially available phenolic resins and commercially available polyimide resins, and It contains either a liquid or powdered polymer resin such as a mixture thereof.

  Additives can be in the form of powders, fibers, flakes, liquids, or porous substrates composed of one or more fibers, membranes, metal meshes, and foams.

  There are various ways to mix together the polyimide precursor, carbon, and other components. For example, in the case of a polyimide precursor, one mixing method is to mix the polyimide powder with carbon and other additives as a whole. Another method is to coat a viscous solution of poly (amic acid) over carbon and other additives before removing the solvent and then convert the poly (amic acid) to polyimide. The present invention is directed to one embodiment where the polyimide precursor powder is simply mixed with carbon and other additives, but is limited to a specific method of mixing the precursor with carbon and other additives. Is not intended.

  Organic precursors comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole, preferably used in the method of making the monolithic porous carbon disk of the present invention are imidazopyrrolone, siloxane, silica, While other components can be incorporated during the synthesis of epoxies, bismaleimides, polyetherimides, etc., preferably the composition of polyimide and / or polybenzimidazole is greater than or equal to 70% by weight. Have.

  Preferred aromatic tetracarboxylic dianhydrides, or tetracarboxylic acids, or diesters of tetracarboxylic acid monomers preferably used in the use of the method of making the polyimide precursor of the present invention include the following anhydride compounds: Including tetracarboxylic acid derivatives and dialkyl esters of tetracarboxylic acid: pyromellitic dianhydride; pyromellitic acid tetracarboxylic acid, dialkyl ester of pyromellitic acid tetracarboxylic acid and aromatic tetracarboxylic dianhydride or Tetracarboxylic acid or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone dianhydride, 2,3,6,7-naphthylenetetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid, 2,2-bis (3,4-dicarboxypheny ) Propanoic acid dianhydride, and esters of tetracarboxylic acids including combinations thereof.

  When the ester is an alkyl ester, the alkyl group preferably contains 1 to 5 carbon atoms, more preferably a methyl group.

  Preferred aromatic diamine monomers suitably used in the method of making the polyimide precursor of the present invention are 1,4-phenylenediamine, m-phenylenediamine, 4,4′diamino-biphenyl, 4,4 ′ and 3,3 ′. -Diaminodiphenylmethane, 4,4 'and 3,3'-diaminobenzophenone, benzidine, 2,6-diaminopyridine, 2,6-diaminonaphthalene, 1,4-diaminocyclohexane, 2,4 and 2,6-diaminotoluene And derivatives thereof (ie: substituted diamines with substituents). The above diamine monomers can be used alone or as a mixture of two or more thereof.

  Preferred polyamine compounds having more than two amine groups that are suitably used in the method of making the polyimide precursor of the present invention are 3,3 ′, 4,4′-biphenyltetraamine (TAB), 1,2,4. , 5-benzenetetraamine, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4′-tetraaminobenzophenone, 3, , 3 ′, 4-triaminodiphenyl, 3,3 ′, 4-triaminodiphenylmethane, 3,3 ′, 4-triaminobenzophenone, 1,2,4-triaminobenzene, 3,3 ′, 4,4 '-Biphenyltetraamine tetrahydrochloride, 1,2,4,5-benzenetetraamine tetrahydrochloride, 3,3', 4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3 ' 4,4′-tetraaminodiphenylmethane tetrahydrochloride, 3,3 ′, 4,4′-tetraaminobenzophenone tetrahydrochloride, 3,3 ′, 4, -triaminodiphenyl trihydrochloride, 3,3 ′, 4 , -Triaminodiphenylmethane trihydrochloride, 3,3 ', 4, -triaminobenzophenone trihydrochloride, 1,2,4-triaminobenzene trihydrochloride, melamine, 2,4,6-triaminopyrimidine (TAP) These mono-, di-, tri-, or tetra-acid salts such as The acid salts of the above compounds are usually present in the form of hydrated compounds. Any of the above compounds can be used alone or as a mixture of two or more thereof.

  Also, preferred polyamine compounds having more than two amine groups that are suitably used in the method of making a polyimide precursor comprising the three-dimensional molecular structure of the present invention include polyamine oligomers having the formula:

  Preferred aromatic isocyanate monomers suitably used in the method of making the polyimide precursor of the present invention are 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate. including. Any of the above compounds can be used alone or as a mixture of two or more thereof.

  Preferred aromatic dialdehyde monomers suitably used in the method of making the polybenzimidazole precursor of the present invention are isophthalaldehyde, tetraphthaldicarboxaldehyde, phthalic dicarboxaldehyde, and 2, 6-naphthalene dicarboxyaldehyde (2,6-naphthalene dicarboxylaldehyde).

  Preferred aromatic acid monomers and esters of dicarboxylic acids preferably used in the method of making the polybenzimidazole precursor of the present invention are isophthalic acid and esters, phthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid And 2,6-naphthalenedicarboxylic acid. This ester may be an alkyl or phenyl ester. When the ester is an alkyl ester, the alkyl group preferably contains 1 to 5 carbon atoms, more preferably a methyl group.

  Preferred aromatic tetraamine monomers suitably used in the method of making the polybenzimidazole precursor of the present invention are 3,3 ′, 4,4′-tetraaminobiphenyl (3,3′-diaminobenzidine); 2,4,5-tetraaminobenzene; 1,2,5,6-tetraaminonaphthalene; 2,3,6,7-tetraaminonaphthalene; 3,3 ′, 4,4′-tetraaminodiphenylmethane; 3 ', 4,4'-tetraaminodiphenylethane; 3,3', 4,4'-tetraaminodiphenyl-2,2-propane; and combinations thereof.

  Preferred reaction solvents for the synthesis of precursors comprising either polyimide or polybenzimidazole or both polyimide and polybenzimidazole are N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide (DMAc ), N, N-dimethylformaldehyde (DMF), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, methanol, toluene, chlorobenzene, ethanol, and mixtures thereof.

  The monolithic carbon of the present invention is suitable for use as an electrode material for electrochemical capacitors and associated electrochemical devices. The porous monolithic carbon of the present invention offers the advantages of monolithic structure, high density, high surface area, and narrow pore size distribution.

Example 1 Synthesis of a polyimide precursor having a three-dimensional molecular structure and this carbon disk

  Starting monomers: 3,3 ', 4,4'-biphenyltetraamine (TAB), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), and 1,4-phenylenediamine (PPD).

  Solvent: N, N-dimethylacetamide (DMAc).

  1.30 grams (0.012 mole) of PPD was dissolved in 40 ml of DMAc in a flask. While stirring, 3.270 grams (0.015 mol) of solid PMDA was added to the reaction system. After the PMDA was completely dissolved, 0.3215 grams (0.0015 mole) TAB was added to the reaction system. The reaction was carried out at ambient temperature with mechanical stirring until a very viscous solution, often a gel mass, was formed. The temperature of the reaction was gradually increased to 150 ° C. with vigorous stirring to produce a precipitated powdery polyimide. The solvent was distilled off under vacuum at 50 ° C. The powder was further ground and filtered through a 50 micron size sieve.

  Using a hydraulic press, the polyimide powder was packed into a mold and compressed under a pressure of 5000 psi at ambient temperature to produce a monolithic disk. A monolithic carbon disk was produced by pyrolyzing the monolithic disk under nitrogen protection at 800 ° C. for 3 hours. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s showed that the material capacitance was 90 F / gram. See FIG.

Example 2 Synthesis of a polyimide prepolymer having a three-dimensional molecular structure doped with 1% by weight molybdenum and the carbon disk

  Initiating monomers and additives: 3,3 ′, 4,4′-biphenyltetraamine (TAB), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD) ), And molybdenum (V) chloride (MoCl5).

  Solvent: N, N-dimethylacetamide (DMAc).

  1.30 grams (0.012 mole) of PPD and 0.135 grams of MoCl5 were dissolved in 40 ml of DMAc in a flask. While stirring, 3.270 grams (0.015 mol) of solid PMDA was added to the reaction system. After PMDA was completely dissolved, 0.3215 grams (0.0015 mole) of TAB was added to the reaction system. The reaction was carried out at ambient temperature with mechanical stirring until a very viscous solution, often a gel mass, was formed. The reaction temperature was gradually raised to 150 ° C. with vigorous stirring to produce precipitated powdery polyimide / MoCl 5. The solvent was distilled off under vacuum at 50 ° C. The powder was further ground and filtered through a 50 micron size sieve.

  The polyimide powder was consolidated at ambient temperature at a pressure of 4500 psi to produce a monolithic disk. The monolithic disk was pyrolyzed under nitrogen protection at 800 ° C. for 3 hours to produce a monolithic carbon disk. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s showed a material capacitance of 210 F / gram. See FIG.

Example 3 Synthesis of 1% by weight molybdenum doped polyimide prepolymer and future carbon disk

  Starting monomers and additives: 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCl5).

  Solvent: N, N-dimethylacetamide (DMAc).

  1.622 grams (0.015 mol) of PPD and 0.135 grams of MoCl5 were dissolved in 40 ml of DMAc in a flask. While stirring, 3.270 grams (0.015 mol) of solid PMDA was added to the reaction system. The reaction was carried out at ambient temperature with stirring until a very viscous solution was formed. The reaction temperature was gradually raised to 150 ° C. with vigorous stirring to form a precipitated powdery polyimide / MoCl 5 precipitate. The solvent was distilled off under vacuum at 50 ° C. The powder was further ground and filtered through a 50 micron size sieve.

  The polyimide powder was consolidated at ambient temperature at a pressure of 4500 psi to produce a monolithic disk. The monolith was pyrolyzed in a nitrogen atmosphere at 800 ° C. for 2 hours and in a carbon dioxide atmosphere for 1 hour. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s indicated that the material capacitance was 200 F / gram. This is shown in FIG.

EXAMPLE 4 Synthesis of a polyimide precursor doped with 1% (by weight) molybdenum in acetone and this carbon disk

  Initiating monomers and additives: 3,3 ′, 4,4′-biphenyltetraamine (TAB), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD) ), And molybdenum (V) chloride (MoCl5).

  Solvent: Acetone

3. 270 grams (0.015 mole) of PMDA was dissolved in 20 ml of acetone. 1.30 grams (0.012 mole) PPD, 0.3215 grams (0.0015 mole) TAB, and 0.135 grams MoCl5 were dissolved in 20 ml acetone in a separate flask. . The PMDA solution was gradually added to the PPD / TAB / MoCl ₅ solution to quickly form a white precipitate. The solvent was distilled off and the temperature of the product was raised to 150 ° C. to change the poly (amic acid) to powdered polyimide. The powder was further ground and filtered through a 50 micron size sieve.

  The polyimide powder was consolidated at a pressure of 4000 psi at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed under nitrogen protection at 800 ° C. for 3 hours to produce a monolithic carbon disk. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s indicated that the material capacitance was 100 F / gram.

Example 5 Synthesis of a polyimide precursor having a three-dimensional molecular structure doped with 1% by weight molybdenum and this carbon disk

  Initiating monomers and additives: 3,3 ′, 4,4′-biphenyltetraamine (TAB) 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD) , And molybdenum chloride (V) (MoCl5).

  Solvent: N, N-dimethylacetamide (DMAc)

  1.082 grams (0.01 mole) PPD, 0.218 grams diaminopyridine (0.002 mole) and 0.135 grams MoCl5 were dissolved in 40 ml DMAc in a flask. While stirring, 3.270 grams (0.015 mol) of solid PMDA was added to the reaction system. After PMDA was completely dissolved, 0.3215 grams (0.0015 mole) of TAB was added to the reaction system. The reaction was carried out at ambient temperature with normal stirring until a viscous solution was formed. The temperature of the reaction was raised to 150 ° C. with vigorous stirring to produce a precipitated powdery polyimide / MoCl 5. The solvent was distilled off under vacuum at 50 ° C. The powder was further ground and filtered through a 50 micron size sieve.

  The polyimide powder was consolidated at a pressure of 4000 psi at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed under nitrogen protection at 800 ° C. for 3 hours to produce a monolithic carbon disk. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s indicated that the material capacitance was 100 F / gram.

Example 6 Synthesis of polyimide prepolymer and this porous carbon

  Starting monomers: 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) and 1,4-phenylenediamine (PPD).

  Solvent: N, N-dimethylacetamide (DMAc).

  1.622 grams (0.015 mol) of PPD was dissolved in 40 ml of DMAc in a flask. While stirring, 3.270 grams (0.015 mol) of solid PMDA was added to the reaction system. The reaction was carried out at ambient temperature with stirring until a very viscous solution was formed. The reaction temperature was raised to 150 ° C. with vigorous stirring to produce a polyimide precipitate. The solvent was distilled off under vacuum at 50 ° C. The powder was further annealed at 300 ° C. for 30 minutes.

  The polyimide powder was consolidated at a temperature of 4500 psi at ambient temperature to produce a monolith. The monolith was pyrolyzed at 900 ° C. for 3 hours under nitrogen protection. Cyclic voltammetry of the carbon disc at a scan rate of 5 mV / s showed that the material capacitance was 80 F / gram.

Example 7 Supercapacitor Electrode A supercapacitor was constructed using the carbon prepared in Example 3 as an electrode. The electrode dimensions were 0.81 ″ diameter and 0.012 ″ thickness. The prototype supercapacitor comprises a pair of carbon electrodes sandwiched between two current collector plates. A microporous separator was placed between the two electrodes. Before sealing the current plate with the thermoplastic edge sealant, the electrodes and separator were impregnated with 38% sulfuric acid electrolyte. The characteristic results are shown in Table 1.

Table 1

EXAMPLE 8 Synthesis of polyimide precursor doped with 0.5% molybdenum and this porous carbon

  Starting monomers and additives: 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCl5).

  Solvent: tetrahydrofuran (THF)

  3. 270 grams (0.015 mole) of PMDA was dissolved in 20 ml of THF. 1.62 grams (0.015 mole) of PPD and 0.065 grams of MoCl5 were dissolved in 20 ml of THF in a separate flask. The PMDA solution was gradually added to the PPD / MoCl5 solution to quickly produce a white precipitate. The solvent was distilled off. Poly (amic acid) powder was converted to polyimide by thermal annealing at 300 ° C. for 30 minutes.

  The polyimide powder was consolidated at a temperature of 4500 psi at ambient temperature to produce a monolith. The monolith was pyrolyzed at 900 ° C. for 3 hours under nitrogen protection to produce monolithic carbon. Cyclic voltammetry of the carbon disk at a scan rate of 5 mV / s indicated that the material capacitance was 150 F / gram.

Example 9a Preparation of a carbon-carbon composite and its electrochemical capacitor cell

  Polyimide precursor: prepared in Example 6.

  Carbon black powder: Commercially available carbon black derived from natural sources.

  Activated carbon fiber: A phenolic resin based on carbon fiber.

  1.58 grams of carbon black powder (66%), 0.68 grams of polyimide powder (28%), and 0.14 grams of carbon fiber (6%) were ground and mixed, and 0.5 grams of The mixture was compressed at 6500 psi at ambient temperature to produce a monolithic disk about 1 mm thick and 2.5 cm in diameter. The disk was pyrolyzed at 800 ° C. for 3 hours under nitrogen protection to produce a porous carbon-carbon disk.

  According to the procedure of Example 3, a symmetrical single cell was assembled using two carbon-carbon composite disks 2.5 cm in diameter, 1.20 mm thick and 0.78 grams in weight. The characteristic results are listed in Table 2. The impedance data for the Z "versus Z 'plot is shown in FIG.

Example 9b Comparative Electrochemical Capacitor Battery Comparison Example Using Carbon Black Electrode

  Two carbon discs with a diameter of 2.5 cm, a thickness of 1.20 mm, and a weight of 0.78 grams were prepared from the same carbon black powder used in Example 9a. A symmetrical single cell was assembled using this disk by the procedure of Example 3. The characteristic results are shown in Table 2. The impedance data for the Z "versus Z 'plot is shown in FIG.

Table 2

Example 10 Preparation of a carbon-carbon composite doped with 0.85% molybdenum and this electrochemical capacitor cell

  Polyimide precursor: prepared in Example 1.

  Carbon black powder: commercially available carbon black derived from natural sources;

  Activated carbon fiber: phenolic resin based on carbon fiber;

  Molybdenum chloride (V) (MoCl5).

  0.06 grams of molybdenum chloride was dissolved in 3.0 ml of methanol. Prior to removing methanol by distillation, 2.6 grams of carbon black powder was stirred overnight and immersed in a Mo / methanol solution.

  Grind and mix 1.24 grams of carbon black powder (61%) doped with Mo, 0.665 grams of polyimide powder (33%), and 0.12 grams of activated carbon fiber (6%). , Mixed. 0.5 grams of the mixture was compressed at 6500 psi at ambient temperature to produce a monolithic disk approximately 1 mm thick and 2.5 cm in diameter. This disk was pyrolyzed for 1.5 hours under nitrogen protection at 800 ° C. and 1.5 hours under carbon dioxide protection to produce a porous carbon-carbon composite disk.

  According to the procedure of Example 3, a symmetrical single cell was assembled using two carbon-carbon composite disks 2.5 cm in diameter, 1.20 mm thick and 0.78 grams in weight.

  Thus, the present invention has been described.

FIG. 1 is a graph of cyclic voltammetry (CV) of Example 1 showing C (F / gram) versus voltage at a scan rate of 5 mV / sec. FIG. 2 is a graph of cyclic voltammetry (CV) of Example 2 showing C (F / gram) versus voltage at a scan rate of 5 mV / sec. FIG. 3 is a graph of cyclic voltammetry (CV) of Example 3 showing C (F / gram) versus voltage at a scan rate of 5 mV / sec. FIG. 4 is the impedance data for samples 9a and 9b at a 0.75 V bias level using a sulfuric acid electrolyte. The black line is the capacitor data of sample 9a, and the red line is the capacitor data of sample 9b.

Claims (32)

In the process of producing a monolithic porous carbon disk as an electrode material from a precursor comprising either powdered polyimide or polybenzimidazole, or both polyimide and polybenzimidazole:
Preparing a precursor powder comprising either polyimide or polybenzimidazole, or both polyimide and polybenzimidazole;
Consolidating the precursor powder into a monolith under pressure;
Pyrolyzing the monolith in an inert or carbon dioxide atmosphere to form a monolithic porous carbon disk;
A manufacturing process characterized by comprising:   2. The process of claim 1 wherein a metal compound is added to the precursor during any step used to prepare the precursor powder or monolithic disk.   The process according to claim 1, wherein the precursor is prepared as a powder precipitate in the presence of a solvent.   2. Process according to claim 1, characterized in that the precursor powder for compacting into a disk has an average particle size in the range of 1 [mu] m to 200 [mu] m.   The process according to claim 1, wherein the precursor powder before being consolidated into a disk is annealed at a temperature in the range of 150 ° C to 500 ° C.   The process of claim 1 wherein the prepolymer powder is consolidated under a pressure in the range of 3000 psi to 13000 psi. Process according to claim 1, wherein the monolithic carbon disk has a density in the range of 0.4 grams / cc to 1.2 g / cc, and 300 meters ² / gram, or a larger surface area than 300 meters ² / gram Process characterized by that.   The process according to claim 2, wherein the metal compound is Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Zn, Pb, Hf, W, A process comprising a metal selected from the group consisting of Ba, Al, Pt, Si, P, Rh, Sb, Sn, Bi, Li and combinations thereof.   The process according to claim 2, wherein a metal compound is added to the prepolymer to form an accurate molecular solution of the metal compound having the precursor reaction system.   3. The process of claim 2, wherein the addition of the metal compound to the prepolymer comprises adding a metal compound solution to the dry prepolymer in the form of either a powder or compacted disk, and then removing the solvent from the prepolymer. A process characterized by being performed by.   The process according to claim 2, wherein the weight percentage of metal in the carbon is from 0.01% to 20%.   2. The process of claim 1 wherein an aromatic diamine monomer is used to form the precursor polyimide segment, which is 1,4-phenylenediamine, m-phenylenediamine, 4,4′diamino-biphenyl, 4,4. '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, benzidine, 2,6-diaminonaphthalene, 2,6- A process characterized in that it is selected from diaminopyridine, and derivatives thereof, or combinations thereof.   2. The process of claim 1 wherein an aromatic dianhydride monomer is used to form the precursor polyimide segment, which is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetra. Carboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,6,7-naphthylenetetracarboxylic dianhydride, 1,4,5,8-naphthalene A process characterized in that it is selected from tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, and combinations thereof.   The process of claim 1, wherein the aromatic tetracarboxylic acid ester and acid monomer used to form the precursor polyimide segment are pyrometric tetracarboxylic acids, 3, 3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'benzophenone tetracarboxylic acid, 2,3,6,7 naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid , And combinations thereof, wherein the process is selected from esters of aromatic tetracarboxylic acids and alkyl monomers, including alkyl or phenyl esters having an alkyl group containing from 1 to 5 atoms. 2. The process of claim 1, wherein a polyamine compound having more than two amine functional groups is used to form the precursor polyimide segment, which comprises 3,3 ′, 4,4′-biphenyltetraamine (TAB). ), 1,2,4,5-benzenetetraamine, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4 '-Tetraaminobenzophenone, 3,3', 4-triaminodiphenyl, 3,3 ', 4-triaminodiphenylmethane, 3,3', 4-triaminobenzophenone, 1,2,4-triaminobenzene, 3 , 3 ′, 4,4′-biphenyltetraamine tetrahydrochloride, 1,2,4,5-benzenetetraamine tetrahydrochloride, 3,3 ′, 4,4′-tetraaminodiphenyl ether Tetrahydrochloride, 3,3 ′, 4,4′-tetraaminodiphenylmethane tetrahydrochloride, 3,3 ′, 4,4′-tetraaminobenzophenone tetrahydrochloride, 3,3 ′, 4-triaminodiphenyltrihydrochloride Salt, 3,3 ′, 4-triaminodiphenylmethane trihydrochloride, 3,3 ′, 4-triaminobenzophenone trihydrochloride, 1,2,4-triaminobenzene trihydrochloride, melamine, 2,4,6 -Mono-, di-, tri-, tetra-acid salts, such as triaminopyrimidine (TAP) or formula:

A process characterized in that it is selected from polyamine oligomers having   The process of claim 1 wherein an aromatic isocyanate monomer is used to form the precursor polyimide segment, which comprises 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and 4 , 4'-diphenylmethane diisocyanate.   The process of claim 1, wherein an aromatic dicarboxylic acid ester or acid monomer is used to form the precursor polyimide segment, which is isophthalic acid, phthalic acid, terephthalic acid, 1,4 naphthalenedicarboxylic acid. Or a process characterized in that it is selected from 2,6-naphthalenedicarboxylic acid.   2. The process of claim 1 wherein an aromatic dialdehyde monomer is used to form the precursor polybenzimidazole segment, which comprises isophthalaldehyde, terephthaldicarboxaldehyde, diphthalaldehyde phthalate, and 2,6 A process characterized in that it is selected from naphthalene dicarboxyaldehyde, and combinations thereof.   2. The process of claim 1 wherein an aromatic tetraamine monomer is used to form the precursor polyimidazole segment, which is 3,3 ′, 4,4′-tetraaminobiphenyl (3,3′- 1,2,4,5-tetraaminobenzene; 1,2,5,6-tetraaminonaphthalene; 2,3,6,7-tetraaminonaphthalene; 3,3 ′, 4,4′- Tetraaminodiphenylmethane; 3,3 ′, 4,4′-tetraaminodiphenylethane; 3,3 ′, 4,4′-tetraaminodiphenyl-2,2-propane; and combinations thereof Process.   The process according to claim 3, wherein the organic solvent is N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformaldehyde (DMF), dioxane, dimethyl sulfoxide ( DMSO), chlorobenzene, acetone, methanol, and tetrahydrofuran (THF), toluene, benzene, ethanol, 2-propanol, and mixtures thereof. The process of claim 1, wherein the polyimide and polybenzimidazole have the formula:

Here, A1 and A4 are
Bifunctional phenyl, bifunctional biphenyl, selectively substituted aryl, optionally substituted alkylene, optionally substituted heteroaryl, or combinations thereof;
A2 and A5 are
Representing a trifunctional phenyl, biphenyl, an optionally substituted trifunctional aryl group, or an optionally substituted difunctional heteroaryl group;
A3 is
Multifunctional phenyl having a functional group greater than or equal to 2 Multifunctional biphenyl having a functional group greater than or equal to 2 Selectively substituted poly having a functional group greater than or equal to 2 A functional aryl, a selectively substituted polyfunctional alkylene having a functional group greater than or equal to 2, a selectively substituted polyfunctional heteroaryl having a functional group greater than or equal to 2, or A combination of these;
n1, n2, n3 is greater than or equal to 1; (y + 2) is greater than 2 or equal to 2.
A process characterized by having a structure of   2. The process of claim 1 wherein the process further includes solid reinforcing materials or other additives during the consolidation process to produce the monolithic porous carbon disk composite. A process characterized by comprising a step incorporated into.   23. The process of claim 22, wherein the reinforcing material or other additive is one or more types of organic polymer fibers or inorganic polymer fibers or metal fibers, silica, carbon cloth, carbon paper, carbon nanotubes, metal A process comprising a nonwoven or woven reinforcing fiber pad comprising fibers or particles, polymer micron beads, microcrystalline inorganic and organic compounds, silica powder, inorganic filler, liquid polymer resin, or particles.   The process of claim 1, wherein the process further comprises the step of adding carbon to the precursor powder to form a monolithic porous carbon-carbon composite disk.   25. Process according to claim 24, characterized in that the composition of the carbon-carbon composite before pyrolysis is in the range of 5 to 90%.   26. The process according to claim 25, wherein the carbon is activated carbon powder and activated carbon fibers.   A monolithic porous carbon disk made by the method of claim 1.   25. A monolithic porous carbon-carbon composite made by the method of claim 24. An electrochemical device comprising at least one battery, wherein the battery:
Two conductive electrodes;
A porous non-conductive separator disposed between the two electrodes, and an electrolyte occupying a gap between the electrode and the separator,
Electrochemical device characterized in that at least one of said electrodes comprises a monolithic porous carbon or porous carbon composite according to claim 1.   30. The device of claim 29, wherein the battery comprises a capacitor, a supercapacitor, an electrochemical-electrolyte hybrid capacitor, a hybrid battery / supercapacitor system, a lithium battery, a fuel cell, and other types of batteries. Device. In an electrochemical device comprising at least one battery, the battery includes:
Two conductive electrodes;
A porous non-conductive separator disposed between two electrodes, and an electrolyte occupying a gap between the electrode and the separator,
25. Electrochemical device characterized in that at least one of said electrodes comprises a monolithic porous carbon or a porous carbon composite according to claim 24.   32. The device of claim 31, wherein the battery includes a capacitor, a supercapacitor, an electrochemical-electrolyte hybrid capacitor, a hybrid battery / supercapacitor system, a lithium battery, a fuel cell, and other types of batteries. Device.

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